HU201652B - Fungicidal agents containing 7-amino-azolo[1,5-a] pyrimidine derivatives as agents and process for producing 7-amino-azolo[1,5-a] pyrimidine derivatives - Google Patents

Abstract

1. A 7-aminoazolo[1,5-a]pyrimidine of the formula I see diagramm : EP0215382,P11,F1 where R**1 is di-C1 -C10 -alkylamino-C2 -C6 -alkyl phenoxy-C2 -C6 -alkoxy-C2 -C6 -alkyl or, in which the phenyl moiety is unsubstituted or monosubstituted or polysubstituted by straight-chain or branched C1 -C10 -alkyl, phenyl, C1 -C10 -alkoxy, phenoxy, halogen, phenyl-C1 -C4 -alkyl, phenyl-C1 -C4 -alkoxy, di-C1 -C10 -alkylamino or C1 -C10 -alkylphenylamino, R**2 and R**3 are each hydrogen or C1 -C4 -alkyl, and A is =N-, =CH-, =C(C1 -C4 -alkyl)-, =CBR- or =CCl.

Description

FIELD OF THE INVENTION The present invention relates to fungicides containing 7-aminoazolo [1,5-a] pyrimidine derivatives as active ingredients and to a process for their preparation.

It is known that some of the 7-amino-azolo [1,5-a] pyrimidine derivatives, in particular 7-amino-6-phenyl-5-methyl-1,2,4-triazolo [1,5-a] pyrimidine has a therapeutic effect (U.S. Patent 2,553,500).

It is also known that certain 7-aminoazolo [1,5-a] pyrimidine derivatives, in particular 7-amino-6- [4- (tert-butyloxy) butyl] -5-methyl-2-melyl -pyrazolo [1,5-a] pyrimidine - may be used as an antifungal agent (European Patent No. 141,317). However, the fungicidal activity of this drug is limited.

It has now been found that the 7-aminoazolo [1,5-a] pyrimidine derivatives of formula (I) wherein A is nitrogen or = CH-

R 'is a group of formula (a) or (b) wherein

X is a C 2 -C 6 alkylene group,

Q is mono or tri-substituted with C 1 -C 6 alkoxy-C 2 -C 4 alkyl or with phenyl, phenoxy, C 4 -C 10 alkyl or C 1 -C 6 alkoxy, alone or with halogen and / or C 1 -C 3 alkyl; in the case of substituted phenyl,

R ⁴ and R ^{5 are} C 1 -C 10 alkyl;

R ^{2 is C} 1 -C 4 alkyl and R ^{3 is} hydrogen or C 1 -C 4 alkyl is superior to the known compounds with respect to fungicidal activity, especially in the case of fungal spores.

The 7-amino-triazolo [l, 5-a] pyrimidine derivatives of formula (I) may for example be set in a way that substituted (II) beta-ketoester accordingly - R ⁶ C 1-4 alkyl -a proper , With the aminoazole derivative (III) to form a condensation product (V), the hydroxyl group of which is replaced with a halogen atom, and the resulting compound is reacted with ammonia. (Process A) The β-ketoesters of formula (II) may be prepared as described in Organic Synthesis Coll. 1. 248; No. 3,227,388 Disclosure document in the Federal Republic of Germany. The condensation step with the aminoazoles of formula (III) may be carried out in the presence or absence of a solvent. Suitable solvents are, in particular, alcohols such as ethanol, propanol, butanol, glycols or glycol monoethers, diethylene glycol or its monoether; amides such as dimethylformamide, diethylformamide, dibutylformamide, Ν, Ν-dimethylacetamide, low molecular weight alkanoic acids such as formic acid, acetic acid, propionic acid, and mixtures of these solvents with water. The reaction temperature is usually 50 to 300 ° C, preferably 50 to 150 ° C, when working in solution.

The condensation product is mostly pure and, after washing, for example with the solvent or water used, after drying, for example, with phosphorus halides at 50-150 ° C, is preferably halogenated at reflux temperature. A base such as Ν, Ν-dimethylaniline may be used in stoichiometric amounts or in excess of the halogenation.

After evaporation of the excess phosphorus oxychloride, ice water is added to the mixture, optionally with a water immiscible solvent, and optionally the base is removed by extraction with hydrochloric acid.

Finally, the chlorinated product thus obtained is usually very pure and, therefore, it is most convenient to directly convert it with ammonia to a new 7-aminoazolo [1,5-a] pyrimidine derivative. Preferably, it is reacted with 1-10 moles of ammonia, optionally in a solvent, at a pressure of up to 100 bar at a temperature of about 100 ° C.

The novel 7-aminoazolo [1,5-a] pyrimidine derivatives are generally crystalline compounds which can be directly prepared in very pure form.

The 7-aminoazolo [1,5-a] pyrimidine numbers of formula (I) may also be prepared by substitution of the appropriately substituted a-acyl nitrile derivatives of formula (IV) with azoles (Process B) in a solvent or without using a solvent. Solvents and reaction heaters which are recommended in connection with Procedure A are preferably employed. Process B can be used to directly prepare novel 7-amino-azolo [1,5-a] pyrimidine derivatives; which, after evaporation of the solvent and after dilution with water, may be isolated in most cases as highly pure compounds in crystalline form. When low molecular weight alkanoic acids, fatty acids, are used as a solvent, it is convenient to partially evaporate the excess and then neutralize the acid residue.

The α-acyl nitriles required for the preparation of 7-aminoazolo [1,5-a] pyrimidine derivatives are known in part; some unknown α-acyl nitriles can be prepared from known nitriles and carboxylic acid esters having an α-stable hydrogen by known methods using strong bases such as alkali hydrides, alkali amides or metal alkyls [J. Amer. Chem. Soc. 73, 3766 (1951).

Production Example for Procedure A:

Table 97 of the table. Preparation of 7-amino-5-methyl-6- [2- / 2-methoxyethoxy-propyl] -1,2,4-triazolo [1,5-a] pyrimidine

a) Preparation of 7-hydroxy-5-methyl-6- [2- / 2-methoxyethoxy) propyl] -1,2,4-triazolo [1,5-a] pyrimidine

43.6 g of 86% by weight of 2- [2- / 2-methoxyethoxy / propyl] -acetic acid methyl ester (corresponding to 37.5 g of 100% material, ie 161 mmol) ) Was treated with 16.8 g (200 mmol) of 3-amino-1H-1,2,4-triazole in 300 ml of propionic acid for 24 hours at 60 ° C under a nitrogen atmosphere. After cooling, the mixture is stirred in ice water, neutralized with 2N sodium hydroxide solution and any precipitate formed is filtered off. The aqueous phase was extracted four times with methylene chloride, dried and evaporated. The resulting oily material was triturated with diethyl ether and the crystals thus separated were suctioned off and dried. The yield was 17.5 g (41% of the calculated amount), m.p. 127-128 'C. The infrared spectrum showed predominantly 7-oxo-4H tautomer.

b) Preparation of 7-chloro-5-methyl-6- [2- / 2-methoxyethoxypropyl] -1,2,4-triazolo [1,5-a] pyrimidine

16.0 g (56.2 mmol) of the material obtained in step a) are boiled in 300 ml of phosphorus oxy-23 for 20 hours.

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In trichloride. The excess phosphorus oxychloride is then distilled off. The residue was treated first with water and then with aqueous sodium bicarbonate solution. The washed material was extracted several times with methylene chloride and the extract was washed several times with water. After drying and evaporation, 12.5 g of an oily substance (corresponding to a yield of 78% by weight of the product of step a) are obtained which is used without further purification in the following step c). 10

(c) Table No 97 is replaced by the following: preparation of the active ingredient corresponding to the substance of the invention

A solution of 12.0 g (42.1 mmol) of the chlorine compound obtained in step b) (200 ml of dried 1,4-dioxane) is reacted with 460 mmol of gaseous ammonia in an autoclave at a starting pressure of 100 bar for 60 hours. The reaction mixture was cooled and depressurized with water, extracted several times with methylene chloride, dried and evaporated. The residue was triturated with n-pctane. This gives 5.0 g of crystalline material (corresponding to a 45% yield based on the chlorine compound), m.p. 143-144 ° C.

Preparation Example B Process 7-Amino-5-methyl-6- [3- / 2- / 2,4,6-lichlorophenoxy / ethoxylpropyl] -1,2,2 Preparation of 4-triazolo [1,5-a] pyrimidine

a) Preparation of 2-acetyl-5- [2- / 2,4,6-trichlorophenoxy / ethoxy] valeric acid nitrile

Dissolve 5- (2- (2,4,6-trichlorophenoxy) -ethoxy] -valeric acid nitrile (245 g, 760 mmol) in dry tetrahydrofuran (1 L) and cool to -68 ° C under protective gas. 572 ml of a 1.5 molar solution of n-butyllithium in hexane (equivalent to 858 mmol of n-butyllithium) was added dropwise and the mixture was stirred for an additional three hours at -60 ° C. dissolved in tetrahydrofuran (dry) mL (74.0 mL, 66.7 g;

Dry ethyl acetate (758 mmol) was added slowly. The mixture was kept at -60 ° C for an additional three hours and then allowed to warm to room temperature overnight. Cautiously quench the excess bulyl lithium with water and adjust the pH to 4 with 2N hydrochloric acid. The organic phase was separated, washed with water, dried and evaporated. 267 g of a yellow oil are obtained (yield 73% of crude product) which can be used without further purification.

b) Preparation of the active ingredient according to Example 8 of the Table

The total amount of α-acetylnitrile prepared as described above (732 mmol) was combined with 61.5 g (731 mmol) of 3-amino-1H-1,2,4-triazole in 1.0 L of boiling propionic acid for 24 hours. The reaction mixture was allowed to cool and the reaction mixture was evaporated after filtration. The residue is taken up in methylene chloride, washed several times with water - until the aqueous phase is neutral, and the material is dried and evaporated. This gives 166 g of crystalline material (corresponding to a yield of 53% on nitrile), m.p. 193-194 ° C.

Preparation Example 7 Process 7: 7-Amino-5-methyl-6- [2-IN-1,3,5,5-trimethylhexyl-N-methylaminol-ethyl-1,2,4] triazolo! Preparation of 1 H-aspirimidine

a) Preparation of 2-acetyl-4- [N- (3,5,5-trimethylhexyl] -N-methylamino] -butyric acid nitrile

As previously described, 31.3 g (139.5 mmol) of 4- [N / 3,5,5-trimethylhexyl] -N-methylamino] -butyric acid nitrile in 300 ml of dry tetrahydrofuran was first treated with 103 ml of 1.5 mol butyl lithium (154 mmol) followed by 13.7 mL (12.4 g, 141 mmol) of dry ethyl acetate in 50 mL of tetrahydrofuran. The reaction mixture was worked up by adjusting the pH to 6 with 2N hydrochloric acid. After evaporation of the solvents, 33.0 g of an oily substance are left (88% yield of crude product) which can be used without further delay in the next step.

b) Preparation of the active ingredient according to example 125 in the tables

The total amount of nitrile obtained in the previous step (124 mmol) was reacted with 10.4 g (124 mmol) of 3-amino-1H-1,2,435-triazole in 300 ml of boiling propionic acid for 18 hours. After evaporation of the solvent, the residue was triturated with n-pentane and filtered off with suction. The material was taken up in methylene chloride and filtered through a column of silica gel containing 5% (v / v) methanol. The eluate was partitioned between aqueous sodium carbonate, dried and evaporated. This gave 13.0 g of a solid (corresponding to 32% yield on nitrile), m.p. 109-110 ° C.

In the following table, the active ingredients included in one of their properties (melting point, physical state) were prepared by Methods A or B, respectively. Non-characteristic compounds can also be readily prepared by altering the starting materials and employing the manufacturing protocol as appropriate. Based on structural similarity, these compounds can be expected to exert similar effects.

Table 1a)

The compounds of formula (VI) obtainable by the process of the present invention

Compound (RX, -X- Melting Point Serial Number ('C)

H

H

H

H

- (CH

-CH (CH 3) CH ₂ - (CH ₂ ) ₃ - 157-158

- (CH 3

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Ja) Continuation of table

Serial number of compound (Rk X ' melting point CC) 5 H - {CH ^ s- 6 2,4,6-Cl ₃ - (CH ₂ ) z ~ 7 2,4,6-Cl ₃ -CH (CH ₃ ) CH ₂ - 8 2,4,6-Cl ₃ - (CH ^ - 9 2,4,6-Cl ₃ -ÍCH,) - 10 2,4,6-Cl ₃ - (CH ^ j 11 2-C1 - (CHA) are ^ 12 2-C1 -CH (CH ₃ ) CH ₂ - 13 2-C1 - (CH,), - 14 2-C1 - (CH,), - 15 2-C1 - (CH ^ j 16 4-C1 - (CHzV 17 4-C1 -CH (CH ₃ ) CH ₂ - 18 4-C1 - (CH,), - 19 4-C1 -ICHa) ₄ - 20 4-C1 - (Chavan 21 3-C1 - (CH 22 3-0 -CH (CH ₃ ) CH ₂ - 23 3-0 - (CH,), - 135-137 24 3-0 - (CH,), - 25 3-0 - (CHajj- 26 2-Br - (CHA) are a- 27 2-Br -CH (CH ₃ ) CH ₂ - 28 2-Br - (CHa) ₃ - 161-163 29 2-Br - (CHa) ₄ - 30 2-Br - (Chavan 31 4-Br - {Chavan 32 4-Br -CH (CH ₃ ) CH ₂ 33 4-Br - (CHa) ₃ - 34 4-Br - (CH ₂ ) ₄ - 35 4-Br - (-CON) - 36 2-CH ₃ - (CHJa- 37 2-CH ₃ -CH (CH ₃ ) CH ₂ - 38 2-CH ₃ - (CH? - 164-166 39 2-CH ₃ - (CHa) ₄ - 40 2-CH ₃ - (CHA) are 5- 220 (dec.) 41 3-CH ₃ -ÍCHa) z 42 3-CH ₃ -CH (CH ₃ ) CH ₂ - 43 3-CH ₃ - (CHa) ₃ - 147-149 44 3-CH ₃ -ICHa) ₄ - 45 3-CH ₃ - (CHajj- 46 4-CH ₃ - (CH ₂ ) ₂ - 47 4-CH ₃ -CH (CH ₃ ) CH ₂ - 48 4-CH ₃ - (CH 155-158 49 4-CH ₃ - (CH,), - 50 4-CH ₃ - (CH) - 51 2,4,6- (CH ₃ ) ₃ - (CHA) are z- 52 2,4,6- (CH ₃ ) ₃ -CH (CH ₃ ) CH ₂ - 53 2,4,6- (CH ₃ ) ₃ - (CHa) ₃ - 190-191 54 2,4,6- (CH ₃ ) ₃ - (CH ₂ ) ₄ - 55 2,4,6- (CH ₃ ) ₃ - (CH ₂ ) 5- 157-160 56 tert-C ₄ H _{9 CH?} -C (CH _{3) 2} - (CHA) are ^ 57 ter-C ₄ H ₉ -CH a -C (CH ₃ ) ₂ -CH (CH ₃ ) CH ₂ - 58 hi -C ₄ H ₉ -CHH ₃ (CH ₃ ) ₂ - (CHa) ₃ - 59 hi -C (-C1 -CH3 -C1CH3), - (CH3) ₄ 60 ter-C ₄ H ₉ -CH 2 -C (CH ₃ ) ₂ - (Chavan 149-151 61 4-O-2-CH ₃ - (CHa) ₃ - 144-145 62 2- (-C ₃ H ₇ ) - (CHA) are ^ 63 2- (sec-C ₄ H ₉ ) -ICHa) ₃ - 118-120 64 2- (sec-C ₄ H ₉ ) - (CH ^ s- 154-156

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EN 201 652 Β la) Continuation of the table

Serial number of compound (RL X ' melting point (° C) 65 4-C ₆ H ₅ - (CH,) ₃ - 176-179 66 4 CeHj - (CH ^ s- 172-174 67 4-H, C, 0 - (CH,), - 162-163 68 4-H, C, 0 -CH (CH ₃ ) CH ₂ - 158-160 69 4-H, C, 0 - (CHJr- 70 4-H, C, 0 - (CH,), - 71 4-H _s C ₂ O - (CH ^ j 72 4-H, C ₆ O - (CH 73 4-H, C ₆ O -CHíCHjJCHt- 74 4-H, C ₆ O - (CH,) ₃ - 156-158 75 4-H _s C ₆ O -ÍCHaV 76 4-H ₅ C ₆ O - (CH,), - 77 2- (nC, H ₉ ) O - (CH ^ j 133-135 78 2- (nC, H ₉ ) O - (CH,), - 79 2- (nC, H ₉ ) O - (CH,), - 80 3- (nC ₄ H ₉ ) O Λ 81 3- (nC, H ₉ ) O - (CH,), - 82 3- (nC, H ₉ ) O - (CH,), - 83 4- (nC ₄ H ₉ ) O - (CH,), - 84 4- (nC, H ₉ ) O - (CH,), - 85 4- (nC, H ₉ ) O - (CH,), - 92 3- (H, C) N - (CH,) ₃ - 93 S ÍHsCzJN - (CH,) ^

Table lb): The compounds of formula (VII) obtainable by the process of the present invention Serial number of compound (R) N X ' melting point CC) 94th 4-tC, IVCH ₂ -C (CH ₃ ) ₂ - - (CH,) ₃ - 60 95 .. 4-tC, H ₉ -CH, -C (CH ₃ ) ₂ - - (CH,), - oil

Table 2 The compounds of formula (VIIII) obtainable by the process of the present invention Serial number of compound R ' X ' melting point (° C) 96 CH ₃ - (CH,), - 97 ch ₃ -CH (CH ₃ ) CH, - 142-144 98 CH? - (CH ^ j 99 ch ₃ - (CH,), - 100 ch ₃ - (CH,), - 101 n CA - (CH,), ^ 102 Π-C4H9 -CH (CH ₃ ) CH ₂ - 103 Π-C4H9 - (CH,), - 104 Π-C4H9 - (CH,), - 105 nC, H ₉ - (CH,), - 106 2-ethylhexyl - (CH ₂ ) - 107 2-ethylhexyl CH (Me) CH, - 108 2-Ethyl-hcxil - (CH ^ j í

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Continuation of Table 2

The compound is R '

-XOlvadáspont

CC)

109 2-ethylhexyl - (CH3) ₄ - 110 2-ethylhexyl - (CHJj- 111 3,5,5-trimethyl-hexyl - (CH ^ 112 3,5,5-trimethyl-hexyl -CH (CH ₃ ) CH ₂ - 113 3,5,5-trimethyl-hexyl - (CH? - 114 3,5,5-trimethyl-hexyl - (CHJ ₄ - 115 3,5,5-trimethyl-hexyl - (CHJj- 116 nH ₉ C ₄ -O- (CH ₂ ) ₃ - - (CHJj- 117 n-HA-CH ^ j- -CH (CH ₃ ) CH ₂ - resin 118 nH ₉ C ₄ -O- (CH ₂ ) ₃ - - (CHJ ₃ - 119 n-H ₉ C ₄ -O- (CH 3) - (CH? - 120 _n -H ₉ C ₄ -O- (CH ₂ ) ₃ - - (CHJj- 121 n-H ₉ C ₄ -O- (CH ₂ ) 2 - -CH (CH ₃ ) CH ₂ - 122 CHjOÍCHjjx-1 H ₃ C ₂ -CH-nC ₄ H ₉ -CH (CH ₃ ) CH ₂ - 123 (CHJACHJ, 1 HJC-CH-CH-tC? H? -CH (CH ₃ ) CH ₂ -

Table 3 Compounds of formula IX prepared by the process of the present invention Serial number of compound R ⁵ R ⁴ melting point (° C) 124 nC ₆ H ₁₃ - nC ₆ H ₁₃ - 139-140 125 3,5,5-trimethyl-hexyl CH ₃ 109-110

Table 4: The compounds of formula (X) can be prepared by the process of the present invention Serial number of compound R ² R ³ THE melting point cc) 126 H H N 127 ch ₃ ch ₃ N 128 ch ₃ ch ₃ CH 129 ch ₃ ch ₃ C-Br

The new active substances have a strong fungicidal action against fungi which cause plant diseases, especially fungi belonging to the class of algae.

The novel compounds are therefore suitable, for example, for controlling the following fungi:

- Phytophthora infestans (in tomato and potato crops);

- Phytophthora parasitica (in strawberry cultures);

- Phytophthora cactorum (in apple orchards);

- Pseudoperonospora cubensis (in cucumber cultures);

- Pseudoperonospora humuli (in hops);

- Peronospora destructor (onion plants);

- Peronospora sparsa (on roses);

- Peronospora tabacina (on tobacco plantations);

- Plasmopara viticola (in vines);

- Plasmopara halstedii (in sunflower fields);

- Sclerospora macrospora (in maize);

- Brcmia lactucac (lettuce);

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EN 201 652 - Mucor mucedo (on fruits);

- Rhizopus nigricans (on beet);

- Erysiphe graminis (in cereals);

- Uncinula necator (in vineyards);

- Podosphaera leucotricha (on apples);

- Sphacrotheca fuliginca (on roses);

- Erysiphe cichoriacearum (in cucumber fields).

Active ingredients are well tolerated by plants Some of the active ingredients have a curative effect, which means that these compounds can be used even in the presence of higher levels of contamination of plants, in order to achieve a definite result as they kill pathogens.

The fungicides contain from 0.1 to 95% by weight, preferably from 0.5 to 901% by weight of the active ingredient. The application rates vary between 0.1 and 5 kg / ha, depending on the desired effect.

The compositions of the invention may also be admixed or applied with other active ingredients such as herbicides, insecticides, growth regulators and other fungicides or fertilizers. In many cases, the fungicidal spectrum can be broadened by mixing with fungicides. More than one of these fungicide blends exhibits efficiency gains:

By way of example, a list of fungicides which may be combined with the new formulation is given below:

- sulfur;

- dithiocarbamates and their derivatives, such as:

Ferric dimethyl dithiocarbamate;

Zinc dimethyl dithiocarbamate;

Zinc ethylene bis-dithiocarbamate;

- manganese ethylene bis-dithiocarbamate;

- manganese zinc ethylene diamine bis-dithiocarbamate;

Tetramethylthiuram disulfide;

A complex of zinc / N, N'-ethylene bisdilocarbamate / ammonia;

Zinc / N, N'-propylene bis-dithiocarbamate / ammonium complex;

- zinc / N, N'-propylene-bis-dithiocarbamal;

-?,? - propylene bis thiocarbamoyl disulfide;

- nitro derivatives such as:

* Dinitro- (1-methyl-heptyl) -phenyl-crotonate;

- 2- (sec-butyl) -4,6-dinitrophenyl-3/3-dimethylacrylic;

- 2- (sec-butyl) 4,6-dinitrophenyl isopropyl carbonate;

- diisopropyl ester of 5-nitroisophthalic acid, - heterocyclic compounds such as:

- 2-heptadecyl-2-imidazoline acetate;

- 2,4-dichloro-6- (o-chloroanilino) -s-triazine;

- 0,0-diethyl phthalimido phosphonothioate;

5-amino-1- [bis (dimethylamino) phosphinyl] -3-phenyl-1,2,4-triazole;

- 2,3-dicyano-1,4-dithioanthraquinone;

- 2-thio-1,3-dithio- [4,5-b] -quinoxaline;

- 1- (butylcarbamoyl) -2-benzimidazole-carbamic acid methyl ester;

- 2-methoxycarbonylamino-benzimidazole;

- 2- (furyl) - (2) -benzimidazole;

- 2- (thiazolyl) -4-benzimidazole;

- N- (1,1,2,2-tetrachloroethylthio) -tetrahydrophthalimide;

- N- (trichloromethyl) phthalimide;

- N- (dichlorofluoromethylthio) -N ', N'-dimethyl-N-phenyl-sulfuric acid diamide;

5-ethoxy-3- (trichloromethyl) -1,2,3-thiadiazole;

- 2- (rhodanomethylthio) benzothiazole;

- 1,4-dichloro-2,5-dimethoxybenzene;

- 4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone;

Pyridine-2-thioxo-1-oxide;

- 8-hydroxyquinoline or its copper salt;

- 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxatin;

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxatin-4,4-dioxide;

2-methyl-5,6-dihydro-4 H -pyran-3-carboxylic acid anilide;

2-methylfuran-3-carboxylic acid anilide;

--2,5-dimethyl-furan-3-carboxylic acid anilide;

2,4,5-trimethyl-furan-3-carboxylic acid anilide;

- 2,5-dimethyl-furan-3-carboxylic acid cyclohexylamide;

- N-cyclohexyl-N-methoxy-2,5-dimethyl-furan-3-carboxylic acid amide;

- 2-methyl-benzoic anilide;

2-iodo-benzoic anilide;

- N-formyl-N-morpholine-2,2,2-trichloroethyl acetal;

Piperazine-1,4-diylbis [1,2,2,2-trichloroethyl] -formamide;

- 1- (3,4-dichloroanilino) -1- (formylamino) -2,2,2-trichloroelane;

- 2,6-dimethyl-N-tridecylmorpholine and salts thereof;

- 2,6-dimethyl-N-cyclododecylmorpholine, or salts thereof;

- N - [3- (p-tert-butylphenyl) -2-methylpropyl] -cis-2,6-dimethylmorpholine;

- N - [3- (p-tert-butyl-phenyl) -2-methyl-propyl] -piperidine;

- 1- (2- (2,4-dichlorophenyl) -4-ethyl-1,3-dioxolan-2-yl-ethyl) -1H-1,2,4-triazole;

1- (2- (2,4-dichlorophenyl) -4-n-propyl-1,3-dioxolan-2-yl-ethyl) -1H-1,2,4-triazole;

- N- (n-propyl) -N- (2,4,6-trichlorophenoxyethyl) -N'-imidazol-yl-urea;

- 1- (chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanone;

- 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanol;

- alpha- (2-chlorophenyl) -alpha- (4-chlorophenyl) -5-pyrimidine methanol;

5-butyl-2- (dimethylamino) -4-hydroxy-6-methylpyrimidine;

Bis (p-chlorophenyl) pyrimidine methanol;

- 1,2-bis-3-ethoxycarbonyl-2-lioureido / benzene;

- 1,2-bis (3-methoxycarbonyl-2-thioureidc) benzene;

- 2-cyano-N- (ethylaminocarbonyl) -2- (methoxyimino) -acetamide;

- and various fungicides such as:

Dodecyl guanidine acetate;

- 3- (3- (3,5-dimethyl-2-oxycyclohexyl) -2- (hydroxycyclyl) -glutarimide;

- hexachlorobenzene;

DL-methyl-N- (2,6-dimethylphenyl) -N-furoyl (2) -alaninate;

- DL-N- (2,6-dimethylphenyl) -N- (2'-methoxyacetyl) -alanine methyl ester;

- N- (2,6-dimethylphenyl) -N- (chloroacetyl) -D, L-2-aminobyrrolactone;

5-methyl-5-vinyl-3- (3,5-dichlorophenyl) -2,4-dioxo-1,3-oxazolidine;

- 3- (3,5-dichlorophenyl) -5-methyl-5- (methoxymethyl) -1,3-oxazolidin-2,4-dione;

- 3- (3,5-dichlorophenyl) -1-isopropylcarbamoylhydantoin;

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EN 201 652 Β - N- (3,5-Dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboxylic acid imide.

The novel compositions may be formulated, for example, in the form of directly sprayable solutions, emulsions, aqueous, oily or other dispersions of the active ingredient in high concentrations, pastes, dusts, sprays and granules by spraying, dusting, spraying, spraying or irrigation. The choice of use depends entirely on the intended use; the application form should, as a general rule, ensure that fine distribution of the active substances is possible

For use in the preparation of solutions, emulsions, pastes and oily dispersions, either directly or after emulsification in water, medium to high spinning petroleum fractions, such as kerosene or diesel oil, and coal tar oils, etc., and vegetable or animal oils, aliphatic, cyclic or aromatic benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalene derivatives or derivatives of these compounds such as methanol, ethanol, propanol, butanol, chloroform, tetrachlorocarbons, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., highly polar e.g. dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, water and the like. come into consideration.

Aqueous uses include emulsion concentrates, pastes, wettable powders (sprayable pores), oily dispersions which can be prepared by the addition of water. For the preparation of emulsions, pastes or oily dispersions, the materials may be used as they are, dissolved in oils or solvents; wetting agents, tackifiers, dispersants and emulsifiers can be homogenized in water. However, these agents may also be formulated with more effective materials: wetting agents, tackifiers, dispersants or emulsifiers, and optionally solvents or oils, which may be diluted with water.

Suitable surfactants include lignin sulfonic acids, naphthalenesulfonic acids, phenolsulfonic acids, alkyl aryl sulfonates, alkyl sulfates, alkali metal, alkaline earth metal and ammonium salts, alkali metal salts of dibutylnaphthalenesulfonic acid, and of alkali metal salts of dibutylnaphthalenesulfonic acids, alkali metal and alkaline earth metal salts of fatty acids, sulfate hexadecanol, heptadecanol, octadecanol salts, sulfate fatty alcohol glycol ether salts, sulfonated naphthalene or sulfonated naphthalene derivatives, condensates with naphthalene and formaldehyde, N-octyl phenol ether, ethoxylated isooctyl phenol, octyl phenol, nonyl phenol, alkyl phenol polyglycol ether, tributyl phenyl polyglycol ether, alkyl aryl polyether alcohol, isotridecyl alcohol, fatty alcohol and ethylene oxide condensation product, ethoxylated castor oil, polyoxyethylene / alkyl ether, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol ester, lignin, sulphite impurity and methylcellulose.

Sponges, dusts and spray formulations may be prepared by mixing or co-grinding the active ingredients with a solid carrier.

Granules, such as coated, impregnated or homogeneous granules, may be prepared by attaching the active ingredient to a solid carrier with the aid of a binder. Solid carriers include minerals such as silica gel, silicas, silica gels, silicates, talc, kaolin, clay, limestone, chalk, bolus, loess, attaclay, dolomite, diatomaceous earth, calcium carbonate, magnesium sulfate, magnesium sulfate, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, carbanide and plant materials such as cereal flour, bark, wood flour, walnut powder, cellulose powder and other solid carriers may be used.

Examples of such pesticides include:

I. 90 parts by weight of the compound of Example 3 are mixed with 100 parts by weight of N-methylpyrrolidone. In this way, a solution is obtained which can be used in the form of smaller drops.

II. 20 parts by weight of the active ingredient of Example 8 are dissolved in a mixture having the following composition:

80 parts by weight of xylene;

10 parts by weight of an addition compound prepared by reaction of monoethanolamide with ethylene oxide in a 1: 8-10 molar ratio of clegyenck;

5 parts by weight of calcium salt of dodecylbenzenesulfonic acid; and

- 5 parts by weight of an addition compound prepared by reacting a 40: 1 molar mixture of ethylene oxide and castor oil.

When this solution is poured into water and finely divided, an aqueous dispersion is obtained.

III. 20 parts by weight of the active ingredient obtained according to the procedure of Example 23 are dissolved in a mixture having the following composition:

- 30 parts by weight of cyclohexanone;

- 30 parts by weight of isobutanol;

- 20 parts by weight of an addition compound prepared by reacting a 40: 1 molar mixture of ethylene oxide and castor oil

When this solution is poured into water and mixed with water, an aqueous dispersion is obtained.

ARC. 20 parts by weight of the active ingredient prepared according to the procedure of Example 38 are dissolved in a mixture having the following composition:

- 25 parts by weight cyclohexanol ·,

65 parts by weight of a petroleum fraction of 21G-280 ° C; and

-10 parts by weight of an addition compound made from a 40: 1 molar mixture of ethylene oxide castor oil. When this solution is poured into water and mixed with water, an aqueous dispersion is obtained.

V. 20 parts by weight of the compound prepared according to Example 43 are well mixed with 3 parts by weight of sodium salt of diisobutylnaphthalene-alpha-sulfonic acid, 17 parts by weight of lignin-sulfonic acid sodium salt prepared from sulphite waste and 60 parts by weight of silica gel. we go crazy in a hammer mill.

If this mixture is finely dispersed in water, a pcrmcle juice is obtained.

VI. 5 parts by weight of the compound prepared according to Example 94 are intimately mixed with 95 parts by weight of 815 parts.

GB 201 652 Β parts with finely powdered kaolin. In this way, a spray containing 5% by weight of active ingredient is obtained.

VII. 30 parts by weight of the active ingredient obtained in Example 117 are intimately mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil sprayed on the surface of this silica gel. In this way, the active ingredient is formulated in a form with good adhesion.

Vin. 40 parts by weight of the compound prepared according to Example 124 are intimately mixed with 30 parts by weight of sodium salt prepared from the condensation product of phenolsulfonic acid, urea and formaldehyde, 2 parts by weight of silica gel and 48 parts by weight of water. In this way, a stable aqueous dispersion is obtained.

IX. 20 parts by weight of the active compound prepared according to Example 23 are intimately mixed with 2 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of polyglycol fatty alcohol, 2 parts by weight of paraffinic oil prepared from condensation product of phenolsulfonic acid, urea and formaldehyde. In this way, a stable oily dispersion is obtained.

The following examples demonstrate the biological activity of the new compounds To enable comparisons, data from two known active substances are also provided: 7-amino-6-phenyl-5-melyl-1,2,4-triazolo [1,5-a] pyrimidine (A) (U.S. Patent 2,553,500) and 7-amino-6- (4-tert-butyloxy) -5-methyl-2-methylpyrazolo [1,5-a]. ] pyrimidine (B) (European Patent No. 141,317).

Example 1: Efficacy against Plasmopara viticola

The leaves of the "Müller-Thurgau" grapes in the pot are sprayed with a sprayer containing 80% active ingredient and 20% emulsifier (sodium lignin sulfonate) based on dry matter. In order to evaluate the duration of action of the active ingredients, the plants are placed in a greenhouse for 10 days after the spray has dried. Only then are the leaves inoculated with a slurry of Plasmopara viticola (grapevine spores). Subsequently, the grapes are first placed in a 24 'C water-saturated chamber for 16 hours, and finally for 8 days in a greenhouse where the temperature is maintained between 20' C and 30 'C. After this time, the plants are again placed in a humid chamber for 16 hours to speed up the process. Then, on the underside of the leaves, the fungal infested portion is evaluated.

The results of the experiment show that when the spray contained 0.05% by weight of the active compounds 3, 8, 23, 38, 43, 94, 117 and 124, the fungicidal effect was higher. (97%) as if the spray had the same amount of active ingredient A or B (60%).

Example 2: Efficacy against Phytophthora infestans on tomatoes The leaves of "Grosse Fleischlomate" (large, fleshy tomato) tomato (pot) were sprayed with an aqueous spray containing 80% by weight of active ingredient and 201% of emulsifier (sodium lignin sulphate) . After the spray juice had dried, the leaves were infected with a zoospore suspension of Phytophthora infestans. The plants were then placed in a steam-saturated chamber and the temperature of the chamber maintained between 16 and 18 'C. After 5 days, the disease developed on untreated but infected control plants to such an extent that the fungicidal activity of the active compounds could be evaluated.

The results of the experiment show that when the spray contained 0.05% of the active ingredient of Examples 8, 63 and 124, it showed a better (97%) effect than if the spray contained the known active ingredient B (0%).

Claims (2)

PATENT CLAIMS CLAIMS 1. A fungicidal composition comprising 0.1-95% by weight of the 7-aminoazolo [1,5-a] pyrimidine derivative of the formula I as active ingredient A is N; R ¹ is a group of formula (a) or (b), wherein X is C2-C6 alkylene, Q is (C 1 -C 6) alkoxy (C 2 -C 4) alkyl or phenyl optionally substituted with C 1 -C 6 alkyl or 1 to 3 halogens, R ⁴ and R ⁵ are C 1 -C 10 alkyl, R ² is C 1 -C 4 alkyl, and R ^{3 is} hydrogen together with the usual excipients. 2. A process for the preparation of the 7-aminoazolo [1,5-a] pyrimidine derivatives of the formula I wherein N is or = CH-, R ^! a group of the general formula (a) or (b) in which X is a C 2 -C 6 alkylene group, C 1 -C 6 -alkoxy) -C 2 -C 4 -alkyl or mono-or tri-substituted with phenyl, phenoxy, C 4 -C 10 alkyl or C 1 -C 6 alkoxy in the case of substituted phenyl, R ⁴ and R ^{5 are} C 1 -C 10 alkyl; R ^{2 is C} 1 -C 4 alkyl and R ^{3 is} hydrogen or C 1 -C 4 alkyl, characterized in that: a) (II) beta-ketoester - ^R1 and ^R2 are as defined above, R ⁶ C 1-4 alkyl - amino azole derivative (III) - A and R ³ are as defined above - converting it into a condensation product of formula (V) - R ¹ , R ² , R ³ and A are as defined herein - the hydroxyl group of this compound is replaced by a halogen atom and the resulting compound is reacted with ammonia; obsession b) The alpha-acyl nitrile derivative of formula IV is reacted with an aminoazole of formula III in which R ¹ , R ² , R ³ and A are as defined herein.